Improving the dye lightfastness of acrylic substrates with triazine compounds

ABSTRACT

A method of improving the dye lightfastness of acrylic polymer substrates by the incorporation of amino or hydroxy-substituted triazine compounds. Preferred Polymers comprise polyacrylonitrile and copolymers containing at least 80 percent acrylonitrile. Preferred lightfastness agents are triamino triazine and trihydroxy triazine in amounts from about 0.2 percent to about 5 percent, based on polymer weight.

United States Patent Pilling [s41 IMPROVING THE DYE LIGHTFASTNESS OFACRYLIC SUBSTRATES WITH TRIAZINE COMPOUNDS [72] Inventor: Brlan Pllllng,1309 Elizabeth Ave. SE,

Decatur, Ala. 35601 [22] Filed: Aug. 3, 1966 21 Appl. No.: 569,796

[52] US. Cl "8/4, 260/41 C, 260/45.8 N, 8/165 [5 I Int. Cl. ..D06p 3/00,D06p 5/00, D06p 5/02 [58] Field of Search ..8/55 A, 74, 165,4; 260/41 C,260/418 [56] References Cited Jan. 25, 1972 FOREIGN PATENTS ORAPPLICATIONS 6,410,105 3/1965 Netherlands .l ..260/41 C OTHERPUBLICATIONS Journal of the Textile Institute, April 1965, p. 84;Abstract of 8.1. 978,605

Primary ExaminerNorman G. Torchin Assistant Examiner-John WinkelmanAnorney kobert L. Broad, Jr. and Roy P. Wymbs [5 7] ABSTRACT triazineand trihydroxy triazine in amounts from about 0.2

percent to about 5 percent, based on polymer weight.

w 7 Claims, NoDrawir'ig Figures IMPROVING THE DYE LIGHTFASTNESS OFACRYLIC SUBSTRATES WITH TRIAZINE COMPOUNDS This invention concerns thefading of colored substrates comprised of acrylic polymers. Morespecifically, the invention relates to a process of improving thelightfastness of colored substrates comprised of an acrylic polyme Thechange in hue of colored substrates is a coin 'nob'servation when thesubstrates are subjected to w'a thering'and' sunlight. This phenomenonis commonly known as fading. Explanation of this fading or change in huehas been the subject of extensive research.

To prevent the fading of colored substrates, the textile industry haschemically treated these substrates with film forming agents to protectthe outer layer of the substrate and to prevent the ingress of solarrays. Also, the industry has chemically modified the dyes and thesubstrates to produce more color stable dyes and substrates.

It has been discovered that the introduction of a triazine compound intoan acrylic polymer improves the lightfastness of a colored substrateformed from the acrylic polymer.

It is therefore an object of this invention to provide a process forimproving the lightfastness of a colored substrate comprised of anacrylic polymer.

It is also an object of this invention to provide a colored substratecomprised of an acrylic polymer which exhibits improved lightfastnesscharacteristics.

Other objects of this invention will become apparent as the invention isfully developed within the specification.

These and other objects of this invention are accomplished by providinga process of improving the lightfastness of a colored substratecomprised of an acrylic polymer comprising introducing into said polymera triazine compound of the formula:

wherein R is selected from the group consisting of NH and -OH.

The term substrate as used herein is defined asa film, a woven fabric, anonwoven fabric, a filament, and any article comprised of an acrylicpolymer.

As mentioned previously, the substrate is comprised of an acrylicpolymer. The acrylic polymer may be defined as a polymeric material suchas polyacrylonitrile, copolymers including binary and ternary polymerscontaining at least 80 percent by weight of acrylonitrile in the polymermolecule, or a blend comprising polyacrylonitrile or copolymerscomprising acrylonitrile with from 2 to 50 percent of another polymericmaterial, the blend having an overall polymerized acrylonitrile contentof at least about 80 percent by weight. While the preferred polymersemployed in the instant invention are those containing at least about 80percent of acrylonitrile, generally recognized as the fiber-formingacrylonitrile polymers, it is to be understood that the invention islikewise applicable to acrylic polymers containing less than 80 percentacrylonitrile, e.g., polymers containing from about 35 percent to about80 percent acrylonitrile.

For example, the acrylic polymer can be a copolymer of from about 80percent to about 98 percent acrylonitrile and from about 2 percent toabout percent of another monomer containing the C=O linkage andcopolymerizable with acrylonitrile. Suitable mono-olefinic monomers,include acrylic, alphachloroacrylic and methacrylic acids; the acrylatessuch as methylmethacrylute. cthylmethacrylate, butylmethacrylate,methoxylmethyl methacrylate. betachloroethyl methacrylate, and thecorresponding esters of acrylic and alphachloroacrylic acids; vinylchloride, vinyl fluoride, vinyl bromide, vinylidene chloride,l-chloro-l-bromo-ethylene; methacrylonitrile; acrylamide andmethacrylamide; alpha-chloroacrylamide and monoalkyl substitutionproducts thereof; methylvinyl ketone; vinyl carboxylates such as vinylacetate, vinyl chloroacetate, vinyl propionate, and vinyl sterate;N-vinylimides such as N- vinylphthalimide and N-vinyl-succinimide;methylene malonic esters; itaconic acid and itaconic esters;N-vinylcarbazole; vinyl furane; alkylvinyl esters; vinyl sulfonic acid;ethylene alpha, betadicarboxylic'acids and their anhydrides orderivatives thereof such as diethylcitraconate, diethylmesaconate;styrene; vinyl naphthalene; vinyl-substituted tertiary heterocyclicamines such as the vinylpyridines and alkyl-substituted vinylpyridinesfor example 2-vinylpyridine, 4-vinylpyridine, 2- methyl-S-vinylpyridine,etc.; l-vinylimidazole and alkyl-substituted l-vinylimidazoles such as2-, 4-, or S-methyl-lvinylimidazole; and other i containingpolymerizable materials.

The polymer may be a ternary or higher interpolymer, for example,products obtained by the interpolymerization of acrylonitrile and two ormore of any of the monomers, other than acrylonitrile, enumerated above.More specifically the ternary polymer can be comprised of acrylonitrile,methacrylonitrile and 2-vinylpyridine. The ternary polymer preferablycontains from about percent to about 98 percent of acrylonitrile, fromabout 1 percent to about l0 percent of a vinylpyridine or al-vinylimidazole, and from about I percent to about 18 percent ofanother substance such as methacrylonitrile, vinyl bromide or vinylchloride.

The polymer may also be a blend of a polyacrylonitrile or of a binaryinterpolymer of from about 80 percent to about 99 percent acrylonitrileand from about 1 percent to about 20 percent of at least one other U==Ccontaining substance with from about 2 percent to about 50 percent ofthe weight of the blend of a copolymer of from about l0 percent to about70 percent of acrylonitrile and from about 30 percent to about percentof at least one other containing polymerizable monomer. Preferably, whenthe polymeric material comprises a blend, it will be a blend of acopolymer of from about 90 percent to about 98 percent acrylonitrile andfrom about 2 percent to about 10 percent of another mono-olefinicmonomer, such as vinyl acetate, with a sufficient amount of a copolymerof from about 10 percent to about 70 percent of acrylonitrile and fromabout 30 percent to about 90 percent of a vinyl-substituted tertiaryheterocyclic amine, such as vinylpyridine or l-vinylimidazole, to give adyeable blend having an overall vinyl-substituted tertiary heterocyclicamine content of from about 2 percent to about 10 percent based on theweight of the blend.

The triazine compounds useful with the invention are identified by theformula:

wherein R is selected from the group consisting of NH; and -OH. Thetriazine nucleus can have R groupings consisting of all NH or all OHgroupings or any combination of these two groupings. Preferred triazinecompounds include triamino triazine (melamine) and trihydroxy triazine(cyanuric acid).

As mentioned previously, the triazine compound is introduced into theacrylic polymer. Introduction can be effected by any method whichintimately mixes the triazine compound with the acrylic polymer. Forexample, the triazine compound can be introduced by mixing it with theacrylic polymer in solution for about 30 minutes at room temperature.Shorter and longer mixing periods and higher and lower temperatures arealso useful in the mixing.

The amount of the triazine compound useful in the invention should bewithin the range of from about 0.2 percent to about 5 percent, thepercents based on weight of the acrylic polymer. The preferred range isfrom about 0.5 percent to about 1.5 percent of the triazine compound.

The exact character or nature of the final product effected by thetriazine compound and the acrylic polymer is not known. It is knownhowever that the incorporation of the triazine compound improves thelightfastness of a substrate comprised of an acrylic polymer.

As previously mentioned, the substrate is colored. Coloration can beeffected by coloring the substrate with an acid dye, a disperse dye, ora basic dye. introduction of the triazine compound does not produce anyundesirable colorations other than that attributed to added coloringmatter.

To illustrate specific embodiments of the invention, the followingexamples are presented. Where the testing of the samples is reported asPercent Fade, the results are obtained by determining the originaloptical density of the sample (unexposed to light radiation), radiatingwith a light source the sample for a period of time (graduated in hours)and then calculating the percent fade by taking the change (decrease) inoptical density and expressing it as a percentage of the originaloptical density of the unexposed sample. The optical densities of thesamples are determined by using a Cary Recording Spectro Photo Meter,Model 11 MS, Serial No. 125, manufactured by Applied PhysicsCorporation, 2724 South Peck Road, Monrovia, Calif. Radiation with alight source is accomplished by using a Atlas Fade-O-Meter, type FDA-R,Serial No. 2933, manufactured by Atlas Electrical Devices Co., Chicago,lll. The optical density of the sample is a quantitative measure of theamount of the hue or the colorant in the sample and the percent changein optical density or percent fade is a direct measurement of the amountof colorant destroyed or the change in lightfastness of a coloredsample.

Where the testing of the samples is reported as Lightfastness Rating,"the testing is done in accordance with AATCC Tentative Test Method No.l6E-l964T, entitled Colorfastness to Light. This method is described inthe Technical Manual of the American Association of Textile Chemists andColorists, Volume 40, pages B-76 & 8-77, Howes Publishing Co., lnc. 44East 23rd St., New York, N. Y. I965). In this test the samples aresubjected to radiation from a water-cooled xenon-arc lamp and theresulting fading is determined by using the International Geometric GrayScale for evaluating the change in color; this gray scale is explainedon pages 3-56 -B58 of the above manual. A rating of 4 indicates a betterlightfastness rating than 3. Where percents are used in the followingexamples, they are based on weight unless otherwise specified.

EXAMPLE I To solutions containing dimethyl formamide as the solvent andl0 percent, based on weight of polymer per volume of solution, of anacrylic polymer composed of 88 percent of a copolymer being 93 percentacrylonitrile and 7 percent vinyl acetate and 12 percent of a copolymerbeing 50 percent acrylonitrile and 50 percent methylvinyl pyridine,there is added the below indicated percents of triamino triazine(percents based on the weight of the polymer). The resulting solutionsare mixed for 30 minutes at room temperature. Thereafter, l percent(based on the weight of the polymer) of C. l. Acid Blue 104 dissolved indimethyl formamide is added to the solutions and the solutions mixed forminutes at room temperature. Films 0.0l5 inch thick of the abovepolymeric solutions are cast on clean glass plates by using a Gardnerknife and the plates are placed in an oven at l 10- C. for 30 minutes.The films are removed from the plates and mounted on 2 inch X 2 inchblack cards having a 55inch diameter hole punched in one corner of thecard. The original optical density of the film is determined and thefilm is the thereafter radiated with light for a period of time(exposure time). At the end of said period of time the optical densityof the film is again determined. The change in the optical densities isreported as percent fade in Table l. A control sample, i.e., a sampleprepared as described above except the triamino triazine is absent fromthe film, is presented to show the significance of the invention. Theexposure times, the percents of triamino triazine and the percent fadesare indicated in the following table, Table I:

TABLE I Exposure Time Percent Fade These above data show the triaminotriazine (melamine) improves he lightfastness of acrylic films. 1

EXAMPLE 2 To solutions containing dimethyl acetamide as the solvent and15 percent, based on weight of polymer per volume of solution, of anacrylic polymer composed of 93 percent acrylonitrile and 7 percent vinylacetate, there is added the below indicated percents of triaminotriazine (the percents based on weight of the polymer) indicated inTable II. The resulting solutions are mixed for about 20 minutes atabout 60C. The acrylic solutions are then extruded by conventional meansinto filamentary tow and the resulting tow is crimped. Thereafter, thetow samples are colored by immersing them in aqueous dyebaths (liquor togoods ratio 40:1) containing 0.25 percent of a dye indicated in Tablell, 3.0 percent of urea and 5 percent of Glaubers salt. The dyebaths aregradually heated to their boiling points while being agitated and aremaintained at the boil for 60 minutes. The tow samples are removed fromthe dyebaths and scoured for 20 minutes at about 43 C. in aqueoussolutions (liquor to goods ratio 40:l) containing l percent of lgepalCO-7l0 (a nonionic detergent defined as an alkylphenoxypoly(ethyleneoxy)-ethanol, marketed by General Aniline & Film Corp.,Dyestuff & Chemical Div., West 51st St., New York, NY.) and 0.5 percentof trisodium phosphate, the percents based on weight of goods. Thelightfastness of the samples is determined by AATCC Test Method No.l6E1964T. The percents of triamino triazine, the types of dye, and theresults of the lightfastness tests are indicated in Table II (a controlsample is presented for comparison purposes):

TABLE II Lightfastness ratin of Sample colored wit C. I. Basic C. I.Basic Yellow Basic Sample Red 18 15 Blue 22 1 Control 3 3 3 3 3 4 4 3 44 4 4 EXAMPLE 3 The procedure of Example 2 is repeated except the towsamples are colored by immersing them in aqueous dyebaths containing 0.5percent of lgepon T-Sl (sodium N-methyl-N- oleoyl taurate, marketed byGeneral Aniline & Film Corp., Dyestuff & Chemical Div., 140 West SlstSt., New York, N.Y.) and 1 percent of C. l. Disperse Yellow 19. Thedyebaths are heated to about 99 C. over a 45 minute period and aremaintained at this temperature for 60 minutes. The samples are thentreated and tested for lightfastness as described in Example 2. Thepercents of triamino triazine and the results of the lightfastness testsare indicated in Table III:

TABLE III Sample Lightfastness Rating 1. Control 2. 0.2% triaminotriazine 3. 0.5% triamino triazine 4. 1.0% triamino triazine bAAwEXAMPLE 4 To a solution containing dimethyl formamide as the solvent andpercent, based on weight of polymer per volume of solution, of anacrylic polymer composed of 88 percent of a copolymer being 93 percentacrylonitrile and 7 percent vinyl acetate and 12 percent of a copolymerbeing 50 percent acrylonitrile and 50 percent methylvinyl pyridine,there is added 5 percent (based on weight of the polymer) of trihydroxytriazine (cyanuric acid). The resulting solution is mixed for 30 minutesat room temperature. Thereafter, 1 percent (based on weight of thepolymer) of C. I. Acid Blue 104 dissolved in dimethyl formamide is addedto the solution and the solution mixed for 30 minutes at roomtemperature. A 0.015 inch thick film of the polymeric solution is caston a clean glass plate and the plate is placed in an oven at 90 C. for30 minutes. The film is removed from the plate and is radiated for 1hour with a 150-watt Oscham XBO 150 high pressure xenon lamp (marketedby Macbeth Sales Corp., P.O. Box 950-T, Newburgh, N.Y.). Thelightfastness of this test sample is compared with a control sample,i.e., an identical sample treated as above except it does not containthe trihydroxy triazine. Visual inspection shows an improvement inlightfastness of the test sample over the control sample.

It is to be understood that this invention is not to be limited to thespecific embodiments thereof except as defined in the appended claimsbut is useful in as many widely different embodiments without departingfrom the spirit and scope of the invention.

What is claimed is:

l. A process of improving the dye lightfastness of a colored substrateof a polymer containing at least about percent by weight ofacrylonitrile, said substrate being colored with a dye selected from thegroup consisting of acid dyes, disperse dyes and basic dyes, comprisingmixing with said polymer while in solution from about 0.2 percent toabout 5 percent based on the weight of the polymer of a triazinecompound of the formula:

where R is selected from the group consisting NH and OH.

2. The process of claim 1 wherein the triazine compound is triaminotriazine.

3. The process of claim 1 wherein the triazine compound is trihydroxytriazine.

4. The process of claim 1 wherein from about 0.5 percent to about 1.5percent of the triazine compound is mixed with the polymer.

5. A colored substrate having improved dye lightfastness comprised ofthe reaction product of a polymer containing at least 80 percent byweight of a acrylonitrile and from about 0.2 percent to about 5 percentof a triazine compound of the formula:

wherein R is selected from the group consisting of --Nl-l and -OH; anddyed with a member of the group consisting of acid dyes, basic dyes anddisperse dyes.

6. The colored substrate of claim 5 wherein the triazine compound istriamino triazine.

7. The colored substrate of claim 5 wherein the triazine compound istrihydroxy triazine.

2. The process of claim 1 wherein the triazine compound is triamino triazine.
 3. The process of claim 1 wherein the triazine compound is trihydroxy triazine.
 4. The process of claim 1 wherein from about 0.5 percent to about 1.5 percent of the triazine compound is mixed with the polymer.
 5. A colored substrate having improved dye lightfastness comprised of the reaction product of a polymer containing at least 80 percent by weight of a acrylonitrile and from about 0.2 percent to about 5 percent of a triazine compound of the formUla:
 6. The colored substrate of claim 5 wherein the triazine compound is triamino triazine.
 7. The colored substrate of claim 5 wherein the triazine compound is trihydroxy triazine. 